Sulfated metaaminophenol compounds

ABSTRACT

Sulfated metaaminophenols are disclosed and have the formula ##STR1## where: Z is alkyl, aralkyl, monohydroxyalkyl, polyhydroxyalkyl, aryl, aminoalkyl; 
     R 1  is hydrogen, alkyl, monohydroxyalkyl, polyhydroxyalkyl, monocarbamylalkyl, dicarbamylalkyl, aminoalkyl, acylaminoalkyl, carbalkoxyalkyl, carbamyl, or monoalkylcarbamyl; 
     R 2  is hydrogen, alkyl, monohydroxyalkyl, alkoxy; 
     and their acid salts. 
     Intermediate products used for their preparation are also disclosed. 
     These sulfated metaaminophenols are used to dye keratinous fibers.

This application is a divisional of U.S. Ser. No. 08/130,899, filed Oct.4, 1993, now U.S. Pat. No. 5,451,236.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel sulfated metaaminophenols, theintermediate products necessary for their preparation, their use indyeing keratinous fibers, in particular as coupling agents in dyecompositions, and dyeing methods using these compositions.

2. Description of the Prior Art

It is known to dye keratinous fibers, in particular human hair, usingdye compositions containing oxidation dye precursors and couplingagents.

Coupling agents, also known as color modifiers, allow the tints obtainedwith the oxidation dye precursors to be varied.

In the field of dyeing keratinous fibers, in particular human hair,coupling agents are always being sought which, when associated withoxidation dye precursors, will produce a wide range of hair tints with aplay of colors and which have satisfactory resistance to light, washing,bad weather, perspiration and other hair treatments.

The applicant has discovered that novel sulfated metaaminophenols asdefined below when used as coupling agents in oxidation dye compositionsproduce a wide range of tints with a play of colors and which are stableand resistant to light, washing, bad weather, perspiration and otherhair treatments.

One object of the present invention is therefore the provision of novelsulfated metaaminophenols.

The invention also provides intermediate products used in thepreparation of these sulfated metaaminophenols.

Another object of the invention is the use of these metaaminophenols indyeing keratinous fibers, in particular human hair.

The invention further provides oxidation dye compositions for use indyeing keratinous fibers, in particular human hair, containing at leastone ortho and/or para type oxidation dye precursor and at least thesenovel sulfated metaaminophenols as coupling agent.

A still further object of the invention is a method of dyeing keratinousfibers, in particular human hair, using such a composition mixed with anoxidizing agent.

Further objects of the invention will become apparent from thedescription and examples given hereinafter.

SUMMARY OF THE INVENTION

In one aspect the invention consists in novel sulfated metaaminophenolshaving general formula: ##STR2## wherein Z represents a C₁ -C₁₈ alkylradical, an aralkyl radical wherein the alkyl radical is C₁ -C₆, a C₁-C₆ monohydroxyalkyl or C₂ -C₆ polyhydroxyalkyl radical, an arylradical, or an aminoalkyl radical having the formula: ##STR3## wherein nis a whole number from 1 to 6 inclusive; R₃ and R₄, which may beidentical or different, represent a hydrogen atom or a C₁ -C₄ alkylradical, a C₁ -C₄ hydroxyalkyl radical or a C₁ -C₆ acyl radical;

R₁ represents a hydrogen atom, a C₁ -C₆ alkyl radical, a C₁ -C₆monohydroxyalkyl radical, a C₂ -C₆ polyhydroxyalkyl radical, a C₁ -C₆monocarbamylalkyl radical, a C₁ -C₆ dicarbamylalkyl radical, a C₁ -C₆aminoalkyl radical, an acyl(C₁ -C₆)aminoalkyl(C₁ -C₄) radical, acarbalkoxy(C₂ -C₆)alkyl(C₁ -C₄) radical, a C₁ -C₆ carbamyl or monoalkylradical;

R₂ represents a hydrogen atom, a C₁ -C₄ alkyl radical, a C₁ -C₄monohydroxyalkyl radical, or a C₁ -C₄ alkoxy radical,

and their acid salts.

Among the preferred designations for radical Z in sulfatedmetaaminophenols having general formula (I), the C₁ -C₁₈ alkyl radicalmay designate methyl, ethyl, propyl, butyl, dodecyl, or hexadecyl; thearalkyl radical may designate benzyl; the aryl radical may designatephenyl; the mono or polyhydroxyalkyl radical may designate --CH₂ --CH₂OH, --CH₂ --CHOH--CH₂ --OH, --CH₂ --CHOH--CH₃ ; the aminoalkyl radicalmay designate --CH₂ --CH₂ --NH₂, --CH₂ --CH₂ --NHCH₃ ; theacylaminoalkyl radical may designate --CH₂ --CH₂ --NH--COCH₃ ; or##STR4##

When groups R₃ and/or R₄ designate the acyl radical, this latterpreferably signifies the formyl, acetyl or propionyl radicals;

R₂ preferably designates a hydrogen atom or a C₁ -C₄ alkoxy radical.

The corresponding acid salts are preferably selected fromhydrochlorides, sulfates and hydrobromides.

Particular sulfated metaaminophenols having formula (I) which may bementioned are as follows:

2-methoxy 4-methylthio 5-aminophenol

4-methylthio 3-aminophenol

or, in accordance with IUPAC nomenclature:

5-amino 2-methoxy 4-methylsulfanylphenol

3-amino 4-methylsulfanylphenol.

Sulfated metaaminophenols having formula (I) and their cosmeticallyacceptable salts may be prepared in a multistage process.

According to a first process, in a first step a halide of 2-nitro 4-OR₆-benzene, which may be substituted or not, is reacted in the presence ofa base such as potash or potassium carbonate with a thiol having formula(III):

    Z'--SH                                                     (III)

wherein Z' represents a C₁ -C₁₈ alkyl radical, an aralkyl radicalwherein the alkyl radical is C₁ -C₆, a C₁ -C₆ monohydroxyalkyl radical,a C₂ -C₆ polyhydroxyalkyl radical, an aryl radical or a group havingformula (IV): ##STR5## wherein R₃ and n have the meanings indicatedabove for formula (I);

R₅ represents a hydrogen atom or a C₁ -C₃ alkyl radical;

R₆ represents a C₁ -C₁₈ alkyl radical, an aralkyl radical, a silylradical, a pyranyl radical or a hydrogen atom;

in a second step, the nitro substituents on a compound of formula (V):##STR6## reduced to prepare a compound having formula (VI): ##STR7##wherein Z' and R₆ have the meanings indicated above; if necessary,depending on the sulfated metaaminophenol with formula

(I) to be obtained, the following is carried out in a third step:

a) deprotection of the phenolether; or

b) monosubstitution of the aromatic amine to produce a compound offormula (I) where R₁ is other than H; the --OR₆ group may then bedeprotected; or

c) acid hydrolysis of compound (VI) where Z represents ##STR8## toobtain compound (VII): ##STR9## wherein R₃, R₆ and n have the meaningsgiven above, although R₃ may not designate the C₁ -C₆ acyl radical; thenuclear amine may then be monosubstituted and the --OR₆ groupdeprotected; or

d) first substituting the extranuclear amine in compound (VI) where Z'represents the group. (IV) to produce compound (VIII): ##STR10## whereinR₃, R₄, R₆, and g have the meanings given above; the nuclear amine maythen be monosubstituted and the --OR₆ group deprotected.

These steps may be followed by substitution in the benzene ring of a R₂group having the meaning given above although it may not designate ahydrogen atom.

In the first step of a second process a substituted compound havingformula (IX): ##STR11## is reacted with a thiol having formula:

    Z'--SM                                                     (X)

where M is an alkaline radical and Z' has the meaning given above toobtain a compound with formula (XI): ##STR12##

The dioxolane ring of the compound of formula (XI) is opened using analcoholate in a third stage to prepare a compound having formula (XII):##STR13## R₇ represents a linear or branched C₁ -C₄ alkyl group.

Reduction of the nitro groups of compounds (V) or (XII) is preferablycarried out using iron in an acetic medium or by cyclohexene in thepresence of a palladium-carbon catalyst or using powdered zinc in thepresence of ammonium chloride and ethanol or by any other conventionalreduction technique.

Substitution of the aromatic or extranuclear amine may be effected byreaction with ethyl bromide, glycol bromohydrin, ethylchloroformiate,β-chloracetamide or acetic anhydride, for example.

The invention also relates to novel intermediate compounds havingformula (V), (XI) or (XII) as defined above, which can be used in thesynthesis of metaaminophenols having formula (I).

In another aspect the invention consists in the use of at least onesulfated metaaminophenol having formula (I) as defined above in dyeingkeratinous fibers, in particular human hair.

Compounds having formula (I) are applied to the keratinous fibers, inparticular human hair, in a dye composition which constitutes theinvention in a further aspect.

Compositions in accordance with the invention contain at least onesulfated metaaminophenol as defined above in an appropriate dye medium.Preferred compositions contain at least one sulfated metaaminophenol asdefined above as a coupling agent, in association with at least oneortho and/or para type oxidation dye precursor.

The ortho and/or para type dye precursors used in the compositions arecompounds which are not themselves dyes but form a dye by an oxidativecondensation process either with themselves or in the presence of acoupling agent or modifier.

These ortho or para type oxidation dye precursors are benzenederivatives or heterocyclic compounds comprising two functional aminogroups or a hydroxy and an amino group in the ortho or para positionrelative to each other.

Ortho or para type oxidation dye precursors may be selected fromparaphenylenediamines, paraaminophenols, para heterocyclic derivativesof pyridine, pyrimidine or pyrazole such as 2,5-diaminopyridine,2-hydroxy 5-aminopyridine, 2,4,5,6-tetraaminopyrimidine, 4,5-diamino1-methylpyrazole, 2-dimethylamino 4,5,6-triaminopyrimidine,orthoaminophenols and so-called double bases.

Regarding the paraphenylenediamines, compounds having formula (XIII) mayin particular be cited: ##STR14## wherein: R₈, R₉, R₁₀, which may beidentical or different, represent a hydrogen or halogen atom, an alkylradical, an alkoxy radical, or a carboxy, sulfo or hydroxy (C₁ -C₄)alkyl radical;

R₁₁ and R₁₂, which may be identical or different, represent a hydrogenatom, alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl,acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfoalkyl,piperidinoalkyl, morpholinoalkyl or phenyl which may be para substitutedby an amino group; or R₁₁ and R₁₂ together with the nitrogen atom towhich they are bonded form a piperidino or morpholino heterocycle,providing that R₈ or R₁₀ represent a hydrogen atom when R₁₁ and R₁₂ donot represent a hydrogen atom, including the salts of these compounds.The alkyl or alkoxy radicals preferably contain one to four carbon atomsand in particular designate methyl, ethyl, propyl, methoxy and ethoxyradicals.

Particular compounds with formula (XIII) are as follows:

paraphenylenediamine,

p-toluylenediamine,

methoxyparaphenylenediamine,

chloroparaphenylenediamine,

2,3-dimethylparaphenylenediamine,

2,6-dimethylparaphenylenediamine,

2,6-diethylparaphenylenediamine,

2,5-dimethylparaphenylene-diamine,

2-methyl 5-methoxyparaphenylenediamine,

2,6-dimethyl 5-methoxyparaphenylenediamine,

N,N-dimethylparaphenylenediamine,

N,N-diethylparaphenylenediamine,

N,N-dipropylparaphenylene-diamine,

3-methyl 4-amino N,N-diethylaniline,

N,N-di-(β-hydroxyethyl)paraphenylenediamine,

3-methyl 4-amino N,N-di-(β-hydroxyethyl)aniline,

3-chloro 4-amino N,N-di-(β-hydroxyethyl)aniline,

4-amino N,N-(ethyl, carbamylmethyl)aniline,

3-methyl 4-amino N,N-(ethyl, carbamylmethyl)aniline,

4-amino N,N-(ethyl, β-piperidinoethyl)aniline,

3-methyl 4-amino N,N-(ethyl, β-piperidinoethyl)aniline,

4-amino N,N-(ethyl, β-morpholinoethyl)aniline,

3-methyl 4-amino N,N-(ethyl, β-morpholinoethyl)aniline,

4-amino N,N-(ethyl, β-acetylaminoethyl)aniline,

4-amino N-(β-methoxyethyl)aniline,

3-methyl 4-amino N,N-(ethyl, β-acetylaminoethyl)aniline,

4-amino N,N-(ethyl, β-mesylaminoethyl)aniline,

3-methyl 4-amino N,N-(ethyl, β-mesylaminoethyl)aniline,

4-amino N,N-(ethyl, β-sulfoethyl)aniline,

3-methyl 4-amino N,N-(ethyl, β-sulfoethyl)aniline,

N-[(4'-amino)phenyl]-morpholine,

N-[(4'-amino)phenyl]piperidine,

2-hydroxyethylparaphenylenediamine,

fluoroparaphenylenediamine,

carboxyparaphenylenediamine,

sulfoparaphenylenediamine,

2-isopropylparaphenylenediamine,

2-n-propylparaphenylenediamine,

hydroxy-2-n-propylparaphenylenediamine,

2-hydroxymethylparaphenylenediamine,

N,N-dimethyl 3-methylparaphenylenediamine,

N,N-(ethyl,β-hydroxyethyl)paraphenylenediamine,

N-(dihydroxypropyl)-paraphenylenediamine,

N-4'-aminophenylparaphenylenediamine,

N-phenylparaphenylenediamine.

These paraphenylenediamines may be used in the dye composition either inthe form of the free base or as a salt such as the hydrochloride,hydrobromide or sulfate.

Particular p-aminophenols which may be mentioned are as follows:

p-aminophenol,

2-methyl 4-aminophenol,

3-methyl 4-aminophenol,

2-chloro 4-aminophenol,

3-chloro 4-aminophenol,

2,6-dimethyl 4-aminophenol,

3,5-dimethyl 4-aminophenol,

2,3-dimethyl 4-aminophenol,

2,5-dimethyl 4-aminophenol,

2-hydroxymethyl 4-aminophenol,

2-(β-hydroxyethyl) 4-aminophenol,

2-methoxy 4-aminophenol,

3-methoxy 4-aminophenol,

3-(β-hydroxyethoxy) 4-aminophenol,

2-methoxymethyl 4-aminophenol,

2-aminomethyl 4-aminophenol,

2-β-hydroxyethylaminomethyl 4-aminophenol,

2-ethoxymethyl 4-aminophenol,

2-(β-hydroxyethoxy)methyl 4-aminophenol.

The so-called double bases are bis-phenylalkylenediamines correspondingto the formula: ##STR15## wherein: Z₁ and Z₂, which may be identical ordifferent, represent hydroxyl groups or NHR₁₇ groups where R₁₇designates a hydrogen atom or a low alkyl radical;

R₁₄ and R₁₅, which may be identical or different, represent hydrogenatoms, halogen atoms or alkyl radicals;

R₁₃ and R₁₆, which may be identical or different, represent a hydrogenatom, an alkyl or hydroxyalkyl radical or an aminoalkyl radical whereinthe amine moiety may be substituted; Y represents a radical selectedfrom the following:

    --(CH.sub.2).sub.n --, --(CH.sub.2).sub.m --O--(CH.sub.2).sub.m --,

    --(CH.sub.2).sub.q --CHOH--(CH.sub.2).sub.Q --, ##STR16## where n is a whole number between 0 and 8 and m q and p are whole numbers between 0 and 4. This base may also be in the form of addition salts with acids.

The alkyl or alkoxy radicals indicated above preferably designate agroup having one to four carbon atoms, in particular methyl, ethyl,propyl, methoxy and ethoxy.

Particular compounds having formula (IV) which may be mentioned are asfollows:

N,N'-bis-(β-hydroxyethyl) N,N'-bis-(4'-aminophenyl) 1,3-diamino2-propanel,

N,N'-bis-(β-hydroxyethyl) N,N'-bis-(4'-aminophenyl)ethylenediamine,

N,N'-bis-(4-aminophenyl)tetramethylenediamine,

N,N'-bis-(β-hydroxyethyl) N,N'-bis-(4-aminophenyl)tetramethylenediamine,

N,N'-bis-(4-methylaminophenyl)tetramethylenediamine, and

N,N'-bis-(ethyl) N,N'-bis-(4'-amino 3'-methylphenyl) ethylenediamine.

The ortho type oxidation dye precursors are selected fromorthoaminophenols such as:

1-amino-2-hydroxybenzene,

6-methyl 1-hydroxy 2-aminobenzene,

4-methyl 1-amino 2-hydroxybenzene, and

orthophenylenediamines.

The dye compositions described above used to dye keratinous fibers mayalso contain, as well as the coupling agent having formula (I) asdefined above, other known coupling agents such as:

metadiphenols,

metaaminophenols other than those having formula (I),

metaphenylenediamines,

metaacylaminophenols,

metaureidophenols,

metacarbalkoxyaminophenols,

α-napthol,

indole derivatives,

coupling agents containing an active methylene group such as β-ketones,and

pyrazolones.

The following coupling agents may in particular be mentioned:

2,4-dihydroxyphenoxyethanol,

2,4-dihydroxyanisole,

metaaminophenol,

resorcinol monomethylether,

resorcinol,

2-methyl resorcinol,

2-methyl 5-aminophenol

2-methyl 5-N-(β-hydroxyethyl) aminophenol,

2-methyl 5-N-(β-mesylaminoethyl) aminophenol,

2,6-dimethyl 3-aminophenol,

6-hydroxybenzomorpholine,

2,4-diaminoanisole,

2,4-diaminophenoxyethanol,

6-aminobenzomorpholine,

[2-N-(β-hydroxyethyl) amino 4-amino]-phenoxyethanol,

2-amino 4-N-(β-hydroxyethyl) aminoanisole,

(2,4-diamino)phenyl-β-γ-dihydroxypropylether,

2,4-diaminophenoxyethylamine,

1,3-dimethoxy 2,4-diaminobenzene,

1,3,5-trimethoxy 2,4-diaminobenzene,

1-amino 3,4-methylenedioxybenzene,

1-hydroxy 3,4-methylenedioxybenzene,

2-chloro 6-methyl 3-aminophenol,

2-methyl 3-aminophenol,

2-chlororesorcinol,

6-methoxy 3-hydroxyethylaminoaniline,

1-ethoxy 2-bis(β-hydroxyethyl)amino 4-aminobenzene,

3-diethylaminophenol,

1,3-dihydroxy 2-methylbenzene, 1-hydroxy 2,4-dichloro 3-aminobenzene,

4,6-di(hydroxyethoxy) 1,3-diaminobenzene,

4-methyl 6-ethoxy 1,3-diaminobenzene,

4-chloro 6-methyl 3-aminophenol,

6-chloro 3-trifluoroethylaminophenol, and

salts thereof.

Direct dyes may be added to such compositions, as is known in the art,in particular to shade or enrich the lustre of the colors attained bythe oxidation dye precursors. Examples of direct dyes are azo andanthraquinone dyes or nitro compounds of the benzene series.

The total amount of para and/or ortho type oxidation dye precursors plusthe coupling agents used in dye compositions in accordance with theinvention preferably comes to 0.3 to 7% by weight with respect to theweight of said composition. The concentration of sulfatedmetaaminophenols of formula (I) may vary between 0.05 and 3.5% by weightwith respect to the composition weight.

A preferred embodiment of a dye composition also contains a knownanionic, cationic, non-ionic or amphoteric surfactant or mixturethereof.

These surfactants are present in proportions of between 0.5 and 55% byweight, preferably between 2 and 50% by weight with respect to the totalcomposition weight.

These compositions may also contain organic solvents to solubilizecomponents which are insufficiently soluble in water. Particularsolvents which may be mentioned are:

C₁ -C₄ low alkanols, such as ethanol and isopropanol; glycerol;

glycols or glycol ethers such as 2-butoxyethanol, ethyleneglycol,propyleneglycol, diethyleneglycol monoethylether and monomethylether;aromatic alcohols such as benzyl alcohol or phenoxyethanol; analogousproducts, and

mixtures thereof.

The solvents are preferably present in proportions of between 1 and 40%by weight, particularly between 5 and 30% by weight with respect to thetotal composition weight.

Thickening agents may be added to the compositions, for example sodiumalginate, gum arabic, acrylic acid polymers which may be reticulated,cellulose derivatives, or heterobiopolysaccharides such as xanthane gum.Mineral thickening agents such as bentonite may also be used.

The thickening agents are preferably present in proportions of between0.1 and 5%, in particular between 0.2 and 3% by weight with respect tothe total composition weight.

Antioxidants which may be present in the compositions are preferablyselected from sodium sulfite, thioglycolic acid, sodium bisulfite,dehydroascorbic acid, hydroquinone and homogentisic acid. Theseantioxidants are present in the composition in proportions of between0.05 and 1.5% by weight with respect to the total composition weight.

These compositions may further contain other cosmetically acceptableadditives such as penetrating agents, sequestrum producing agents,perfume, buffers, dispersing agents, processing agents, packagingagents, film forming agents, preservatives, opacifying agents, etc.

A composition according to the invention contains a sulfatedmetaaminophenol having formula (I) and an ortho and/or para typeoxidation dye precursor. The composition pH lies between 3 and 10.5. Itis adjusted to the desired value using known alkalizing agents such asammonia, alkaline carbonates, alkanolamines such as mono-, di- andtriethanolamines and their derivatives, or sodium or potassiumhydroxide; or standard acidifying agents, for example mineral or organicacids such as hydrochloric, tartaric, citric or phosphoric acid.

Compositions to be applied to hair may take a number of different forms,for example liquid, cream, gel or any other form appropriate to dyeingkeratinous fibers, in particular human hair. The compositions may bepackaged in aerosol cans with a propellant to produce a foam.

Compounds of formula (I) are used in a method comprising applying acompound having formula (I) and oxidation dye precursors in the presenceof an oxidizing agent to the keratinous fibers, in particular humanhair.

These compounds may be applied simultaneously in a dye composition asdefined above or successively in a multistage method.

Dye compositions in accordance with the invention containing a paraand/or ortho type oxidation dye precursor and a coupling agent offormula (I) are used in a method using an oxidizing agent as developer.

The oxidizing agent is preferably selected from hydrogen peroxide,alkali metal bromates and persalts such as perborates and persulfates.Hydrogen peroxide is particularly preferred.

Using this method, when required for use the dye composition describedabove is mixed with an oxidizing solution in sufficient quantity todevelop the color. The mixture thus obtained is then applied to thekeratinous fibers, in particular human hair.

The pH of the composition applied to the hair preferably varies between2 and 13. It is adjusted to the desired value using known alkalizingagents or acidifying agents as described above. The oxidizing solutioncontains, as the oxidizing agent, hydrogen peroxide, urea peroxide,peroxy salts such as ammonium persulfate, or alkali metal bromides. A 20volume solution of hydrogen peroxide is preferably used.

The mixture obtained is applied to the hair and left for 10 to 40,preferably 15 to 30 minutes. The hair is then rinsed, shampooed, rinsedagain and dried.

The coupling agent of formula (I) defined above may also be used in amultistage method, one step of which consisting in applying the orthoand/or para oxidation dye precursor(s), or a mixture of these, andanother consisting in applying a dye composition containing the couplingagent of formula (I). The oxidizing agent may be introduced into thecomposition just before application in the second step or it may beapplied directly to the keratinous fibers in a third step. Application,pH, washing and drying conditions are as indicated above.

DETAILED DESCRIPTION OF THE INVENTION

The following examples are intended to illustrate but not to limit thescope of the invention.

EXAMPLE 1 Preparation of 4-methylthio-3-aminophenol hydrochloride,denominated in accordance with IUPAC nomenclature as3-amino-4-methlsulfanylphenol hydrochloride.

Step 1: Synthesis of [2-nitro-4-(benzyloxy)phenylmethylsulfane.

65.9 g (0.25 mole) of 1-chloro-2-nitro-4-(benzyloxy)benzene was addedportionwise to a suspension of sodium thiomethylate (0.35 mole) in 100ml dimethoxyethane at room temperature.

The reaction was exothermic. The mixture was cooled to maintain thetemperature between 25° and 30° C. The reaction mixture was poured intoa litre of iced water. The crystalline precipitate was dried then takenup in water.

After recrystallization from 96° ethanol then isopropyl acetate, 34.4 gof orange crystals were obtained which melted at 78° C. Elementalanalysis calculated for C₁₄ H₁₃ NO₃ S was as follows:

    ______________________________________                                        %         C        H      N       O    S                                      ______________________________________                                        Calculated                                                                              61.07    4.76   5.09    17.43                                                                              11.65                                  Found     61.30    4.81   4.90    17.34                                                                              11.57                                  ______________________________________                                    

Step 2: Synthesis of 2-methylsulfanyl-5-(benzyloxy)phenylamine.

A mixture of 2.2 g ammonium chloride, 15 ml water, 140 ml 96° alcoholand 70 g finely powdered zinc was heated under reflux. The[2-nitro-4-(benzyloxy)phenyl]methylsulfane obtained from step 1 wasadded portionwise (33.8 g, 0.123 mole) so as to maintain the refluxwithout heating.

The reduction was exothermic. Following addition, heating under refluxwas continued for 15 minutes.

The decolorized reaction medium was boil filtered. On cooling thefiltrate, pale yellow crystals precipitated which were dried (28.2 g).

Following recrystallization from cyclohexane, this compound melted at64° C. Elemental analysis calculated for C₁₄ H₁₅ NOS was as follows:

    ______________________________________                                        %         C        H      N       O    S                                      ______________________________________                                        Calculated                                                                              68.54    6.16   5.71    6.52 13.07                                  Found     68.40    6.11   5.61    6.72 13.11                                  ______________________________________                                    

Step 3:

The 28.2 g (0.115 mole) of 2-methylsulfanyl-5-(benzyloxy)phenylamineobtained from step 2 was heated at 90°-95° C. in a mixture of 50 ml of36% hydrochloric acid and 5 ml water for one hour.

The suspension was then cooled in an ice bath.

After vacuum drying over potash and recrystallization from absoluteethanol, 8.3 g of white crystals of 3-amino-4-methylsulfanylphenolhydrochloride were obtained which melted with decomposition at 210°-214°C. Elemental analysis calculated for C₇ H₁₀ ClNOS was as follows:

    ______________________________________                                        %         C        H      N       S    Cl                                     ______________________________________                                        Calculated                                                                              43.86    5.26   7.31    16.73                                                                              18.50                                  Found     43.36    5.42   7.08    16.46                                                                              18.26                                  ______________________________________                                    

EXAMPLE 2 Preparation of 2-methoxy-4-methylthio-5-aminophenolhydrochloride, denominated in accordance with IUPAC nomenclature as5-amino-2-methoxy-4-methylsulfanylphenol hydrochloride.

Step 1: Synthesis of 2-methoxy-4-methylsulfanyl-5-nitrophenol.

A suspension of 50.5 g (0.237 mole)methyl-(6-nitrobenzo[1,3]dioxol-5-yl)-sulfane in 230 ml methanol washeated under reflux.

105 ml of a solution of 30% sodium methylate in methanol was addeddropwise.

The heating under reflux was continued for 4 hours.

The mixture was cooled in an ice bath and the sodium phenate of theexpected compound was dried. Following dissolution of the phenate in 2liters of water and acidification with a concentrated hydrochloric acidsolution, the crystalline precipitate was dried, taken up again in waterand dried again.

After recrystallization from isopropanol, 44.5 g of yellow crystals wereobtained which melted at 158° C. Elemental analysis calculated for C₈ H₉NO₄ S was as follows:

    ______________________________________                                        %         C        H      N       O    S                                      ______________________________________                                        Calculated                                                                              44.65    4.21   6.51    29.73                                                                              14.90                                  Found     44.62    4.21   6.42    29.95                                                                              14.72                                  ______________________________________                                    

Step 2: Reduction.

The compound obtained from step 1 (18.8 g-0.0873 mole) was reduced usingthe method described for example 1 step 3, the reaction mixture beingboil filtered into hydrochloric acid in absolute ethanol.

9.6 g of white crystals of 5-amino-2-methoxy-4-methylsulfanylphenolhydrochloride were obtained which melted with decomposition at 235°-240°C. Elemental analysis calculated for C₈ H₁₂ ClNO₂ S was as follows:

    ______________________________________                                        %        C      H        N    O      S    Cl                                  ______________________________________                                        Calculated                                                                             43.34  5.46     6.32 14.43  14.46                                                                              15.99                               Found    43.55  5.52     6.20 14.67  14.22                                                                              15.80                               ______________________________________                                    

EXAMPLES OF COMPOSITIONS EXAMPLE 1

    ______________________________________                                        4-methylthio 3-aminophenol hydrochloride                                                                   0.383 g                                          Paraphenylenediamine         0.216 g                                          Octyldodecanol sold under the trade name                                                                   8 g                                              EUTANOL D by HENKEL                                                           Oleic alcohol                20 g                                             Monoethanolamiine laurylethersulfate sold under                                                            3 g                                              the trade name SIPON LM 35 by HENKEL                                          Ethyl alcohol                10 g                                             Benzyl alcohol               10 g                                             Cetylstearyl alcohol oxyethylenated to 33 moles                                                            2.4 g                                            ethylene oxide sold under the trade name SIMULSOL                             GS by SEPPIC                                                                  Ethylenediamine tetracetic acid                                                                            0.2 g                                            Cationic polymer solution containing the following:                                                        3.7 g                                             ##STR17##                                                                    to 60% M.A.                                                                   monoethanolamine             7.5 g                                            Diethanolamide of linoleic acid sold under the                                                             8 g                                              trade name COMPERLAN F by HENKEL                                              Ammonia solution, 20% NH.sub.3                                                                             10.2 g                                           Sodium metabisulfite, 35% aqueous solution                                                                 1.3 g                                            Hydroquinone                 0.15 g                                           1-phenyl 3-methyl 5-pyrazolone                                                                             0.2 g                                            Demineralized water q.s.p.   100 g                                            ______________________________________                                    

This composition was mixed just before use with an equal weight of 20vol hydrogen peroxide with a pH of 3. The pH of the mixture was-equal to9.5. The mixture was applied to permed gray hair and left for 30 minutesat room temperature. The hair was then rinsed, shampooed and dried. Itwas dyed a dark beige blond.

EXAMPLE 2

    ______________________________________                                        2-methoxy 4-methylthio 5-aminophenol hydro-                                                             0.665  g                                            chloride                                                                      2,6-dimethyl paraphenylenediamine dihydro-                                                              0.627  g                                            chloride                                                                      Oleic alcohol polyglycerolated to 2 moles glycerol                                                      4      g                                            Oleic alcohol polyglycerolated to 4 moles glycerol                                                      5.7    g                                            Oleic acid                3      g                                            Oleic amine oxyethylenated to 2 moles ethylene                                                          7      g                                            oxide sold under the trade name ETHOMEEN                                      012 by AKZO                                                                   Sodium salt of diethylaminopropyl laurylamino                                                           3      g                                            succinamate                                                                   Oleic alcohol             5      g                                            Oleic acid diethanolamide 12     g                                            Propylene glycol          3.5    g                                            Ethyl alcohol             7      g                                            Dipropylene glycol        0.5    g                                            Propylene glycol monomethyl ether                                                                       9      g                                            Sodium metabisulfite, 35% aqueous solution                                                              0.45   g MA                                         Ammonium acetate          0.8    g                                            Antioxidant, sequestrum producer qs                                           Perfume, preservative qs                                                      Monoethanolamine pH: 9.8 qs                                                   Demineralized water qsp   100    g                                            ______________________________________                                    

The above composition was mixed just before use with an equal weight of20 vol hydrogen peroxide whose pH had been adjusted to between 1 and 1.5by addition of orthophosphoric acid (2.5 g orthophosphoric acid per 100g of 20 vol hydrogen peroxide).

The pH of the mixture was equal to 6.5. The mixture was applied to grayhair with 90% white and left for 30 minutes at room temperature. Thehair was rinsed, shampooed, rinsed again then dried. It had been dyed alight blue ash blond.

We claim:
 1. A sulfated metaaminophenol coupler having the formula##STR18## wherein Z represents C₁ -C₁₈ alkyl, aralkyl wherein the alkylmoiety has 1-6 carbon atoms, C₁ -C₆ monohydroxyalkyl, C₂ -C₆polyhydroxyalkyl, aryl, aminoalkyl having the formula ##STR19## whereinn is a whole number ranging from 1 to 6 inclusive, R₃ and R₄, eachindependently, represent hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl orC₁ -C₆ acyl;R₁ represents hydrogen, C₁ -C₆ alkyl, C₁ -C₆ hydroxyalkyl,C₂ -C₆ polyhydroxyalkyl, C₁ -C₆ monocarbamylalkyl, C₁ -C₆dicarbamylalkyl, C₁ -C₆ aminoalkyl, (C₁ -C₆) acylamino(C₁ -C₄)alkyl,carb(C₂ -C₆)alkoxy (C₁ -C₄)alkyl, carbamyl or mono(C₁ -C₆)alkylcarbamyl; R₂ represents hydrogen, C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkyl,or a C₁ -C₄ alkoxy, oran acid addition salt thereof.
 2. The sulfatedmetaaminophenol of claim 1 wherein Z represents methyl, ethyl, propyl,butyl, dodecyl, hexadecyl, benzyl, phenyl, --CH₂ --CH₂ --OH, --CH₂--CHOH--CH₂ --OH, -CH₂ --CHOH--CH₃, --CH₂ --CH₂ --NH₂, --CH₂ --CH₂--NHCH₃, --CH₂ --CH₂ --NH--COCH₃, or ##STR20## and R₂ representshydrogen or C₁ -C₄ alkoxy.
 3. The sulfated metaaminophenol of claim 1wherein said acid addition salt is a hydrochloride, a sulfate or ahydrobromide.
 4. The sulfated metaaminophenol of claim 1 selected fromthe group consisting of2-methoxy-4-methylthio-5-aminophenol and4-methylthio-3-aminophenol.